Liquid vinylidene-terminated polymers cured with amines and thiols

ABSTRACT

Liquid vinylidene (CH 2  ═C&lt;) terminated polymers are prepared by the reaction of a (1) liquid polymer having a terminal functional group selected from the group consisting of carboxyl, hydroxyl, mercaptan, amine and epoxy and (2) a compound containing both an epoxy group ##STR1## and a vinylidene group. The reaction can be catalyzed using a base. The polymers cure readily to solid elastomers which are useful as sealants, caulks, potting compounds, coatings and the like.

This is a division of Application Ser. No. 738,195, filed Nov. 3, 1976,now U.S. Pat. No. 4,129,713, which is a division of Ser. No. 585,962filed June 11, 1975, U.S. Pat. No. 4,013,710; which is a division ofSer. No. 292,926, filed Sept. 28, 1972, which is now U.S. Pat. No.3,910,992.

BACKGROUND OF THE INVENTION

Liquid polymers containing vinylidene (CH₂ ═C<) groups are known. Thesepolymers are prepared in a number of processes such as cleavage ordegradation of high molecular weight dienic elastomers (U.S. Pat. No.3,313,793 and British Pat. No. 1,057,014); the free-radicalpolymerization of dienic monomers in the presence of large amounts of achain transfer agent; the solution polymerization of dienic monomersusing lithium catalysts; and addition methods such as the polyadditionof dithiols with allene (Journal of Polymer Chemistry, Part C, Vol. 24,Page 113 (1968)).

These liquid polymers are cured through the vinylidene groups to solidelastomers. This has advantages in that compounding ingredients may besimply dissolved or dispersed in the polymer by mixing, and thecompounded liquid poured or spread into place. Desirably, the compoundedliquid will then quickly cure in situ at room temperature or with onlyslight application of heat. Unfortunately, the vinylidene groups of thepreviously known polymers are not highly reactive at room temperature.Cure to a dry elastomeric state may often take weeks. This hasheretofore hindered or prevented the use of these liquid polymers inapplications such as commercial caulks and sealants. Furthermore, mostof these liquid polymers have their vinylidene groups pendant to thepolymer backbone. This is not favorable for, in the vulcanized state, anoptimum balance of tensile strength and extensibility is achieved whenthe cure sites are located at the terminal ends of the liquid polymermolecule. This disadvantage cannot be readily remedied as mostpreparation proceses allow for little control over the location of thevinylidene group on the molecule. Liquid polymers containing terminalvinylidene groups are desirable, particularly if the vinylidene groupsare of high activity that readily react with curing agents at roomtemperature to form solid elastomer.

SUMMARY OF THE INVENTION

Liquid vinylidene (CH₂ ═C<) terminated polymers of the structure##STR2## wherein B is a polymeric backbone of carbon-carbon, polyether,or polysulfide linkages; Z is selected from the group consisting of--O--, --S--, --NH--, ##STR3## and --O--CH₂ --CH₂ --; A is a bivalentradical containing 1 to 10 atoms of C, O, S or N; and R is hydrogen oran alkyl radical containing 1 to 4 carbon atoms, cure readily at roomtemperature to a dry surface. The polymers are prepared by the reactionof (1) a liquid polymer having a terminal functional group selected fromthe group consisting of carboxyl, hydroxyl, mercaptan, amine and epoxy,and (2) a compound containing both an epoxy ##STR4## group and avinylidene group. The reaction can be catalyzed using a base.

DETAILED DESCRIPTION

The novel liquid polymers are characterized by having reactive terminalvinylidene (CH₂ ═C<) groups. The polymers have a theoretical reactivevinylidene functionality of 2.0; i.e. one reactive vinylidene group ateach end of the polymer molecule. However, the novelvinylidene-terminated polymers can be prepared from liquid polymerswhich have an average functionality of less than two. Because of this,and also due to incomplete conversions, the novel polymers can have anaverage reactive vinylidene functionality as low as about 1.2. Theliquid polymer reactants used to prepare the novel polymers can alsohave additional carboxyl, hydroxyl, mercaptan, amine, or epoxyfunctional groups as pendant groups. When such a polymer reactant isemployed, the novel polymers can have more than 2, and up to about 12reactive vinylidene groups. Therefore, the novel polymers can have anaverage reactive vinylidene functionality of from about 1.2 to about 12.More preferredly, the novel polymers have an average reactive vinylidenefunctionality of from about 1.6 to about 4.

The liquid vinylidene-terminated polymers have a molecular weight offrom about 1000 to about 20,000 as measured using a Mechrolab VaporPressure Osmometer. The polymers are more conveniently described bytheir bulk viscosity. The polymers have a bulk viscosity of from about500 centipoises to about 8,000,000 centipoises (measured at 27° C. usinga Brookfield model LVT viscometer with spindle No. 7 at 0.5 to 100 rpm).More preferredly, the polymers have a bulk viscosity from about 5000centipoises to about 2,000,000 centipoises. Polymers having a bulkviscosity from about 10,000 centipoises to about 400,000 centipoises areparticularly useful in caulk, sealant, and potting compoundapplications.

The novel polymers are prepared by the reaction of (1) a liquid polymerhaving from about 1.5 to about 12 functional groups per molecule capableof reacting with an epoxy ##STR5## group, and (2) a compound containingboth an epoxy group and a vinylidene group. Liquid polymer reactantshaving terminal functional groups capable of reacting with an epoxygroup include (A) liquid carboxyl-terminated polymers, (B) liquidmercaptan-terminated polymers, (C) liquid hydroxyl-terminated polymers,(D) liquid amine-terminated polymers, and (E) liquid epoxy-terminatedpolymers. These polymers have molecular weights and bulk viscosities inthe same range as described herein for the vinylidene-terminatedpolymers. The functional group, which can be carboxyl, hydroxyl,mercaptan, amine, or epoxy, comprises from about 0.5 percent to about 10percent by weight based upon the weight of the polymer. Morepreferredly, the functional group comprises about 1 percent to about 5percent, by weight of the polymer.

The functionally terminated polymers have polymeric backbones comprisingcarbon-carbon linkages, polyether linkages, or polysulfide linkages. Thepolymers having carbon-carbon linkages contain polymerized units of avinylidene monomer selected from (a) monoolefins containing 2 to about 8carbon atoms such as ethylene, propylene, isobutylene, 1-butene,1-pentene, 1-hexene, and the like; (b) dienes containing 4 to about 10carbon atoms such as butadiene, isoprene, 2-isopropyl-1,3-butadiene,chloroprene, and the like; (c) vinyl aromatics such as styrene, α-methylstyrene, vinyl toluene, and the like; (d) vinyl nitriles such asacrylonitrile, methacrylonitrile, and the like; (e) vinyl and allylesters such as vinyl acetate, vinyl propionate, allyl acetate, and thelike; (f) vinyl and allyl ethers such as vinyl methyl ether, allylmethyl ether, and the like; (g) divinyls and diacrylates such as divinylbenzene, divinyl ether, diethylene glycol diacrylate, and the like; and(h) acrylates of the formula ##STR6## wherein R' is --H, --CH₃ or --C₂H₅, and R" is an alkyl radical containing 1 to 18 carbon atoms or analkoxyalkyl, an alkylthioalkyl, or cyanoalkyl radical containing 2 toabout 12 carbon atoms. Examples of such acrylates are ethyl acrylate,butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate,octadecyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, hexylthioethyl acrylate, β-cyanoethyl acrylate, cyanooctyl acrylate, methylmethacrylate, octyl methacrylte, ethyl ethacrylate, and the like. Oftentwo or more types of polymerized monomeric units are contained in thepolymeric backbone.

Examples of liquid carboxyl-terminated polymers are carboxyl-terminatedpolyethylene, carboxyl-terminated polybutadiene, carboxyl-terminatedpolyisoprene, carboxyl-terminated poly(butadiene-acrylonitrile),carboxyl-terminated poly(butadiene-styrene), carboxyl-terminatedpoly(butadiene-acrylonitrile-acrylic acid), carboxyl-terminatedpoly(ethyl acrylate), carboxyl-terminated poly(ethyl acrylate-n-butylacrylate), carboxyl-terminated poly(n-butyl acrylate-acrylonitrile),carboxyl-terminated poly(butyl acrylate-styrene), and the like. Thepolymers can be prepared by free radical polymerization usingcarboxyl-containing initiators and/or modifiers as disclosed in U.S.Pat. No. 3,285,949 and German Pat. No. 1,150,205, and polymers preparedby solution polymerization using lithium metal or organometalliccompounds and post-treating the polymers to form carboxyl groups asdisclosed in U.S. Pat. Nos. 3,135,716 and 3,431,235. Liquidcarboxyl-terminated polymers as carboxyl-terminated polybutadiene,carboxyl-terminated polybutadieneacrylonitrile, and carboxyl-terminatedpolyacrylate were found to be excellent reactants for the preparation ofthe novel polymers.

Examples of liquid mercaptan-terminated polymers aremercaptan-terminated polybutadiene, mercaptan-terminated polyisoprene,mercaptan-terminated poly(butadiene-acrylonitrile), mercaptan-terminatedpoly(ethyl acrylate), mercaptan-terminated poly(ethyl acrylate-n-butylacrylate), mercaptan-terminated poly(ethyl acrylate-n-butylacrylate-glycidyl acrylate), and the like. The polymers can be preparedby free-radical polymerization of monomers in the presence ofdixanthogen disulfide and then post-reacted to form the mercaptan groupsas disclosed in U.S. Pat. Nos. 3,449,301 and 3,580,830 and British Pat.No. 859,470. They can also be mercaptan-terminated polyethers asdisclosed in Journal of Polymer Science, Vol. 12 (1968), Page 107; andmercaptan-terminated polyalkylene sulfides.

Examples of liquid hydroxyl-terminated polymers are hydroxyl-terminatedpolyethylene, hydroxyl-terminated polybutadiene, hydroxyl-terminatedpolyisoprene, hydroxyl-terminated poly(butadiene-acrylonitrile),hydroxyl-terminated poly(acrylates), and the like. The polymers can beprepared by post-reacting carboxyl-terminated polymers as disclosed inU.S. Pat. Nos. 3,551,471 and 3,551,472; by free-radical polymerizationof monomers using hydroxyl-containing initiators as in U.S. Pat. No.2,844,632; and by solution polymerization using lithium ororganometallic catalysts and post-reacting the product to form thehydroxyl groups as disclosed in U.S. Pat. Nos. 3,135,716 and 3,431,235.

Examples of liquid amine-terminated polymers are the amine-terminatedpoly(2-methyl ethoxy) polymers and the glycol polyamines disclosed inU.S. Pat. No. 3,306,809.

Examples of liquid epoxy-terminated polymers are glycidyl ethers ofpolyhydric alcohols such as glycerol, pentaerithritol, polyvinylalcohol, 1,3,5-trihydroxybenzene, and the like; the glycidyl ethers ofpolyhydric phenols such as bis-phenol A resins and ofphenol-formaldehyde products such as the Novolac resins; and otherepoxies as disclosed in U.S. Pat. No. 3,310,601.

The liquid polymer reactants can contain more than one type offunctional group. For example, the polymer can have terminal carboxylgroups and internal pendant epoxy groups derived from interpolymerizedunits of glycidyl acrylate monomer. Or, the polymer can contain terminalmercaptan groups and internal pendant carboxyl groups derived frominterpolymerized units of acrylic acid.

The novel liquid vinylidene-terminated polymers are prepared in aprocess comprising the reaction of a liquid functionally-terminatedpolymer as described above with a compound containing both an epoxy anda vinylidene group. These compounds have the formula ##STR7## wherein Ris hydrogen or an alkyl radical containing 1 to B 4 carbon atoms, and Ais a bivalent radical containing 1 to about 10 atoms selected from C, O,S and N.

More preferredly, the compound contains a glycidyloxy structure as##STR8## and R is hydrogen or a methyl radical. Examples of the morepreferred compounds are isopropenyl glycidyl ether, allyl glycidylether, methallyl glycidyl ether, glycidyl acrylate, and glycidylmethacrylate. Most preferred are glycidyl acrylate and glycidylmethacrylate.

The liquid vinylidene-terminated polymers have the structure ##STR9##wherein B is a polymeric backbone of carbon-carbon, polyether, orpolysulfide linkages; Z is selected from the group consisting of --O--,--S--, --NH--, ##STR10## and --O--CH₂ --CH₂ --; A is a bivalent radicalcontaining 1 to 10 atoms of C, O, S or N; and R is hydrogen or an alkylradical containing 1 to 4 carbon atoms. The radical Z is the remainingfragment of the hydroxyl group of the hydroxyl-terminated polymeryielding the --O--, the mercaptan group of the mercaptan-terminatedpolymer yielding the --S--, the amine group of the amine-terminatedpolymer yielding the --NH--, the carboxyl-group of thecarboxyl-terminated polymer yielding the ##STR11## or the epoxy group ofthe epoxy-terminated polymer yielding the --O--CH₂ --CH₂ --. The radicalA originates from the compound containing both the epoxy and thevinylidene group. More preferredly, A is ##STR12## which is derived fromthe use of glycidyl acrylate or glycidyl methacrylate, --CH₂ --O--CH₂ --which is derived from the use of allyl glycidyl ether or methallylglycidyl ether, or --CH₂ --O-- which is derived from the use ofisopropenyl glycidyl ether. The polymeric backbone B originates from thepolymeric backbone of the functionally-terminated polymer reactant.

The liquid carboxyl-terminated polymers were found to be excellentpolymer reactants for the reaction. The liquid carboxyl-terminatedpolymers have an average functionality of from about 1.5 to about 12,and more preferredly from about 1.8 to about 4. The averagefunctionality can be determined by multiplying the molecular weight ofthe polymer by the equivalent parts per hundred of carboxyl groups. Themolecular weight can be measured using a Mechrolab Vapor PressureOsmometer. The equivalent parts per hundred of carboxyl groups isdetermined by measuring the weight percent of carboxyl groups in thepolymer (by titration of a polymer solution to a phenolphthaleinend-point using alcoholic KOH) and dividing the resultant figure by 45,the weight of a carboxyl group (--COOH).

The liquid carboxyl-terminated polymers employed have a molecular weightranging from about 1,000 to about 20,000 and a bulk viscosity from about1,000 to about 8,000,000 centipoises, preferably from about 5,000 to2,000,000 centipoises, measured at 27° C. using a Brookfield LVTViscometer with spindle No. 7 at 0.5 to 100 rpm.

The carboxyl-terminated polymers are reacted with a compound containingboth an epoxy and a vinylidene group, at a range of from about 1 mole toabout 3 moles of epoxy to every 1 mole of carboxyl. Use of over 3 molesof epoxy per mole of carboxyl is not necessary to achieve excellentresults.

The reaction can be conducted in bulk, preferably employing an excess ofthe epoxy-vinylidene compound. More preferredly the reaction isconducted in a solvent. The choice of solvent is influenced by thesolubility of the liquid functionally-terminated polymer used. Examplesof useful solvents are aliphatic hydrocarbons such as heptane, hexane,acetone, methylethyl ketone, isopropyl alcohol, t-butyl alcohol, and thelike. Acetone was found to be an excellent solvent for a variety ofliquid polymers.

The reaction temperature is from about 0° C. to about 200° C. A morepreferred temperature range is from about 50° C. to about 150° C. Totalreaction time varies as to the reaction temperature and to the use of acatalyst. A normal reaction time is from about 4 hours to about 24hours. The reaction is preferredly conducted in the absence of air oroxygen.

The reaction rate between the carboxyl group and the epoxy group can beaccelerated by using a base as a catalyst. The base can be an inorganicbase such as sodium hydroxide, potassium hydroxide, and metalalcoholates such as sodium ethoxide, potassium butoxide, and the like.More preferredly, the base is a tertiary amine. The tertiary amine canbe aliphatic, cyclic methyleneamines, or heterocyclic amines. Examplesof these are trimethylamine, triethylamine, triisopropyl amine,dimethylbutyl amine, dimethylbenzyl amine, methyldiphenyl amine,triethanol amine, N-methyl piperidine, N-methyl morpholine,triethylenediamine, pyridine, 4,4'-dipyridyl propane,2,4,6-tri(dimethylaminomethyl)phenol and the like.

The base is used in a range from about 0.05 to about 2 parts by weightbased on 100 parts by weight of the liquid functionally-terminatedpolymer reactant. More preferredly, the base is used at a level fromabout 0.1 part to 1 part by weight.

The vinylidene-terminated polymers can be isolated by direct dryingunder reduced pressure or by coagulation. If a base catalyst isemployed, typically an acid, such as hydrochloric acid, is added toneutralize the base prior to recovery. The solution can be coagulatedusing water, lower alkyl alcohol, or an alcohol/water solution. Thepolymer is then normally washed with water and dried under reducedpressure.

The liquid vinylidene-terminated polymers prepared from thecarboxyl-terminated polymers have Z equal to ##STR13## If glycidylacrylate or glycidyl methacrylate is reacted with thecarboxyl-terminated polymer the radical A is ##STR14## Of course, thepolymeric backbone B is the same as in the carboxyl-terminated reactant.

The liquid polymers have highly reactive terminal vinylidene groups.Therefore, preferredly, they are admixed with an antioxidant to hinderpremature air-oxidation. The antioxidant is used in a range from about0.1 to about 5 parts by weight per 100 parts by weight of polymer. Theantioxidants are typical antioxidants such as phenyl-β-naphthylamine,di-β-naphthyl-p-phenylenediamine, 2,6-di-t-butyl paracresol,2,4,6-trihexyl phenol,1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, and other usefulphenolic antioxidants disclosed in U.S. Pat. No. 3,157,517.

The vinylidene-terminated polymers are cured to solid elastomers usingknown curatives for unsaturated liquid polymers. The curatives includeunsaturated rubber curatives such as sulfur, sulfur donors,tetramethylthiuram disulfide, tetramethylene guanidine, and the like.Because of the high activity of the vinylidene groups, the polymers canreadily cure at room temperature to a dry surface using di- andpolythiols and primary and secondary di- and polyamines. Examples of thethiols are dimercaptans such as 1,4-butane dithiol, 1,7-heptane dithiol,and the like, and thioglycolates and mercaptopropionates such asethylene glycol bis(thioglycolate), trimethyl propanetris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethyleneglycol bis(mercaptopropionate), trimethylol propanetris(mercaptopropionate), pentaerythritol tetrakis(mercaptopropionate),and the like, and other thiols disclosed in U.S. Pat. Nos. 3,310,601 and3,662,023.

Preferredly, the thiol type curatives are used with tertiary amines ascatalysts. Examples of the tertiary amines are trimethyl amine, triethylamine, N,N-dimethylethyl amine, N,N-dimethyl aniline, triphenyl amine,N-methyl piperidine, triethylene diamine, 4,4'-dipyridyl propane,2,4,6-tri(dimethylaminomethyl)phenol, and the like.

Examples of primary and secondary di- and polyamine curatives areethylenediamine, trimethylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine, 1,3-diaminocyclohexane,m-phenylenediamine, bis(hexamethylene)triamine, triethylene tetraamine,hexamethylene tetraamine, tricretonylidene tetraamine, and the like.

The thiol and amine curatives are used in a range from about 0.1 toabout 20 parts by weight per 100 parts by weight of thevinylidene-terminated polymer, and more preferably from about 0.2 toabout 10 parts by weight. If a tertiary amine cure catalyst is employed,the range of use is from about 0.01 to about 3 parts by weight per 100parts of polymer.

Many other compounding ingredients can be used with the liquid polymers.Such ingredients include fillers such as clays, silicas, carbon blacks,resins, asbestos, and the like; plasticizers and extenders such asdiisobutyl oleate, diisooctyl sebacate, dibenzyl phthalate, ASTM oils,glycerin, and the like; antioxidants and stabilizers; pigments such asTiO₂ iron oxide, chromium oxide, and the like; and tackifiers, waxes,fungicides, and the like.

The curatives and compounding ingredients can be admixed with the liquidvinylidene-terminated polymers using internal mixers such as Henschelmixers and extruders or using ink mill rolls, and using standard mixingtechniques.

The liquid polymers can be poured into place, spread into place with aspatula or knife-edge, or forced into place using a caulk gun or thelike. The polymer cures quickly at room temperature, yielding anelastomer having a dry surface. The liquid vinylidene-terminatedpolymers are useful for preparing caulks and sealants for filling cracksand crevices, joints between brick, concrete slabs, glass, and the like;potting compounds for imbedding wires and electrical components;flow-in-place gaskets; and protective coatings for metal, concrete, andthe like.

The following Examples serve to more fully illustrate the invention.Ingredients are given in parts by weight unless otherwise indicated.

EXAMPLE I

Liquid carboxyl-terminated polybutadiene polymers were preparedfollowing the procedure given in U.S. Pat. No. 3,285,949. The polymershad the following properties:

    ______________________________________                                                   Bulk Viscosity                                                                              Weight Percent                                       Polymer    cps @ 27° C.                                                                         Carboxyl Content                                     ______________________________________                                        A          41,400        1.98                                                 B          34,000        2.20                                                 ______________________________________                                    

The polymers were used to prepare liquid vinylidene-terminated polymers.The recipes used and polymer data were as follows:

    __________________________________________________________________________              1   2   3   4   5    6   7                                          __________________________________________________________________________    Polymer A 100 100 100 100 --   --  --                                         Polymer B --  --  --  --  100  100 100                                        Acetone   64  64  64  64  --   64  64                                         Toluene   --  --  --  --  100  --  --                                         Glycidyl acrylate                                                                       8.1 8.1 --  8.1 9.0  9.0 9.0                                        Allyl glycidyl ether                                                                    --  --  7.3 --  --   --  --                                         Trimethyl amine,                                                              milliliters.sup.1                                                                       --  0.8 0.8 0.8 --   0.8 0.8                                        DMP-30.sup.2, parts                                                                     --  --  --  --  1.0  --  --                                         Temperature, °C.                                                                 95  95  95  95  80-95                                                                              95  95                                         Time, hours                                                                             12  12  12  12  16   12   8                                         Vinylidene polymer,                                                           bulk viscosity                                                                cps @ 27° C.                                                                     23,400                                                                            111,800                                                                           24,000                                                                            62,400                                                                            1,800,000                                                                          188,000                                                                           392,000                                    Residual weight                                                               percent carboxyl                                                              content   1.45                                                                              0.02                                                                              0.27                                                                              0.14                                                                              0.09 0.14                                                                              0.29                                       Percent carboxyl                                                              reacted   27  99  86  95  96   94  87                                         __________________________________________________________________________     .sup. 1 25% by weight in methanol                                             .sup.2 2,2,6tri(dimethylaminomethyl) phenol                              

The polymer, solvent, and glycidyl acrylate or allyl glycidyl ether wereplaced in a glass reactor vessel. About 0.5 part by weight based uponthe weight of the polymer of hydroquinone was added to hindercrosslinking reactions. The amine catalyst was then added and thevessels agitated for the times and at the temperatures indicated. Afterreaction, about 0.5 milliliters of concentrated hydrochloric acid wasadded to neutralize the amine catalyst. The vinylidene-terminatedpolymers were isolated by direct drying under reduced pressure.

Sample 1 used no amine catalyst. The carboxyl reacted, but the othersamples demonstrate the accelerated reaction rate obtained by using abase catalyst. The Example shows the preparation of thevinylidene-terminated polymers and shows that high conversions arereadily obtained.

EXAMPLE II

The liquid vinylidene-terminated polybutadiene polymers prepared inExample I were cured using the following recipes:

    __________________________________________________________________________                                                           Con-                                1  2  3  4  5  6  7  8  9  10 11 12 13 14 trol.sup.3             __________________________________________________________________________    Polymer 1    100                                                                              --  --                                                                              -- -- -- -- -- -- -- -- -- -- -- --                     Polmyer 2    -- 100                                                                              -- -- -- -- -- -- -- -- -- -- -- -- --                     Polymer 4    -- -- 100                                                                              -- -- -- -- -- -- 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              --                     Polymer 6    -- -- -- 100                                                                              100                                                                              100                                                                              100                                                                              -- -- -- -- -- -- -- --                     Polymer 7    -- -- -- -- -- -- -- 100                                                                              100                                                                              -- -- -- -- -- --                     Ethylenediamine                                                                            1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.1                                                                              -- -- -- 1.5                                                                              -- -- -- -- -- 1.5                    Triethylene tetraamine                                                                     -- -- -- -- 0.9                                                                              -- -- -- -- -- -- -- -- -- --                     1,6-hexane diamine                                                                         -- -- -- -- -- -- -- 2.6                                                                              -- -- -- -- -- -- --                     Tetramethylene guanidine                                                                   -- -- -- -- -- -- -- -- -- -- -- -- 6  -- --                     Mercaptate P-33.sup.1                                                                      -- -- -- -- -- 8.2                                                                              8.2                                                                              -- -- 4.5                                                                              -- -- -- 4.5                                                                              --                     Methyl tuads.sup.2                                                                         -- -- -- -- -- -- -- -- -- -- 2.5                                                                              -- -- -- --                     Sulfur       -- -- -- -- -- -- -- -- -- -- -- 5  -- -- --                     Zinc oxide   -- -- -- -- -- -- -- -- -- -- 5  -- -- -- --                     DMP-30       -- -- -- -- -- -- 1.0                                                                              -- -- 2.0                                                                              -- -- -- -- --                     Room temperature cure                                                         Days          7  7 10 1  1  7  7  4  1  7  -- -- 7  7  10                     Hardness, Duro A                                                                           -- -- 23  18                                                                               21                                                                              -- --  31                                                                               15                                                                              6  -- -- -- 8  No                     Percent elongation                                                                         40 1000                                                                             275                                                                              400                                                                              200                                                                              450                                                                              175                                                                              225                                                                              500                                                                              350                                                                              -- -- 900                                                                              550                                                                              Cure                   16 hours at 105° C.                                                    Hardness, Duro A                                                                           -- -- -- -- -- -- -- -- --  16                                                                              2  1  1  -- --                     Percent Elongation                                                                         -- -- -- -- -- -- -- -- -- 200                                                                              800                                                                              400                                                                              800                                                                              -- --                     __________________________________________________________________________     .sup.1 Trimethylolpropane tris(mercaptopropionate)                            .sup.2 Tetramethylthiuram disulfide                                           .sup.3 Carboxylterminated polybutadiene used in Example I, 100 parts by       weight                                                                   

The curatives were added to the liquid vinylidene-terminated polymersand the mix stirred to achieve uniform distribution. The mixes were thenpoured into molds and let stand at room temperature to cure. Samples 10to 13 were also cured at elevated temperatures. All of the cured sampleshad dry surfaces. The control sample was an attempt at curing thecarboxyl-terminated polymer from which the vinylidene-terminatedpolybutadiene was prepared. The sample shows that no cure took place,even though the polymer is highly unsaturated and contains pendant vinylstructure as the result of polymerization of the 1,3-butadiene. Thequick, dry cure is achieved only through the reactive vinylidene groups.

Sample 14 was also evaluated by pouring it into a tensile sheet mold andletting it set for seven days at room temperature. The cured tensilesheet was removed and tested for tensile, elongation, and hardessfollowing ASTM D412 and ASTM D676 - Durometer A. The polymer had a 110psig tensile, a 500% elongation, and a Durometer A hardness of 18.

EXAMPLE III

The liquid vinylidene-terminated polymers of the invention have highlyreactive vinylidene groups. In Example II, the control sample, a liquidcarboxyl-terminated polybutadiene polymer did not cure in 10 days eventhough the polymer contains vinyl configuration as the result ofpolymerized 1,3-butadiene. Other liquid polymers having pendant vinylconfiguration were also evaluated. The recipes are as follows:

    __________________________________________________________________________                1  2  3  4  5  6  7  8  9  10                                     __________________________________________________________________________    Polymer 4.sup.1                                                                           100                                                                              -- -- -- -- -- -- -- -- --                                     Polymer 6.sup.1                                                                           -- 100                                                                              -- -- -- 100                                                                              -- -- -- --                                     Hstyl B-1000.sup.2                                                                        -- -- 100                                                                              -- -- -- -- -- -- --                                     Hstyl B-2000.sup.3                                                                        -- -- -- -- -- -- 100                                                                              100                                                                              -- --                                     Hycar 1312.sup.4                                                                          -- -- -- 100                                                                              100                                                                              -- -- -- 100                                                                              100                                    Ethylenediamine                                                                           -- -- -- -- -- 1.5                                                                              5.0                                                                              15.0                                                                             4.25                                                                             8.6                                    Mercaptate P-33                                                                           4.5                                                                              8.2                                                                              31.3                                                                             16.0                                                                             47.0                                                                             -- -- -- -- --                                     DMP-30      2.0                                                                              1.0                                                                               4.0                                                                              2.0                                                                              5.7                                                                             -- -- -- -- --                                     Room temperature cure                                                         Days        7  7  7  7  7  1  7  7  7  7                                      Hardness, Duro A                                                                          6  -- No No No  18                                                                              NO No No No                                     Percent elongation                                                                        350                                                                              175                                                                              Cure                                                                             Cure                                                                             Cure                                                                             400                                                                              Cure                                                                             Cure                                                                             Cure                                                                             Cure                                   16 hours at 105° C.                                                    Hardness, Duro A                                                                           16                                                                              -- No No No -- No No No No                                     Percent elongation                                                                        200                                                                              -- Cure                                                                             Cure                                                                             Cure                                                                             -- Cure                                                                             Cure                                                                             Cure                                                                             Cure                                   __________________________________________________________________________     .sup.1 polymers from Example I                                                .sup.2 Liquid polybutadiene polymer having a molecular weight of about        1200 and about a 90% by weight vinyl configuration                            3Liquid polybutadiene polymer having a molecular weight of about 2100 and     about a 91% by weight vinyl configuration                                     .sup.4 Liquid poly(butadieneacrylonitrile) polymer having about a 32% by      weight acrylonitrile content and about a 20% by weight vinyl configuratio                                                                              

Samples 1, 2 and 6 were prepared using the novel vinylidene-terminatedpolymers. The remaining samples were prepared using liquid polymershaving a high degree of vinyl-configuration unsaturation. Only the novelpolymers cured at room temperature and at elevated temperature, eventhough high levels of curatives were employed with the other polymers.The Example demonstrates that the vinylidene groups of the liquidpolymers of the invention are much more reactive than either mainpolymer chain unsaturation or pendant vinyl unsaturation.

EXAMPLE IV

A liquid carboxyl-terminated poly(butadiene-acrylonitrile) polymer wasprepared following the procedure in U.S. Pat. No. 3,285,949. Theacrylonitrile range of these polymers is from about 1% to about 40% byweight based upon the weight of the polymer, and more preferably is fromabout 10% to about 30% by weight. The butadiene content ranges fromabout 50% to about 98% by weight and the carboxyl content from about0.5% to about 10% by weight, all weights based upon the total weight ofthe polymer. The prepared polymer had a bulk viscosity at 27° C. of112,000, a 2.52% by weight carboxyl content, and a 18.2% by weightacrylonitrile content. The polymer was used to prepare a liquidvinylidene-terminated poly(butadiene-acrylonitrile) polymer. The recipeused and data was as follows:

    ______________________________________                                        Carboxyl polymer         100                                                  Acetone                  64                                                   Glycidyl acrylate        10.3                                                 Trimethyl amine, milliliters                                                                           0.8                                                  Temperature, °C.  95                                                   Time, hours              12                                                   Vinylidene polymer, bulk                                                      viscosity, cps at 27° C.                                                                        300,000                                              Residual Carboxyl content,                                                    weight percent           0.14                                                 ______________________________________                                    

The vinylidene polymer was prepared following the procedure given inExample 1. The polymer was cured using the following recipes. Allsamples had a dry surface.

    ______________________________________                                                       1      2        3                                              ______________________________________                                        Vinylidene polymer                                                                             100      100      100                                        Ethylenediamine           1.7      1.25                                       Triethylene tetraamine                                                                         0.4               1.0                                        Room temperature cure                                                         Days             1        1        1                                          Hardness, Duro A 1        27       30                                         Elongation, percent                                                                            400      100      125                                        ______________________________________                                    

EXAMPLE V

Liquid carboxyl-terminated polyacrylate polymers were prepared followingthe procedure given in U.S. Pat. No. 3,465,058. The polymers made hadthe following properties:

    ______________________________________                                                   Bulk Viscosity                                                                              Weight Percent                                       Polymer    cps at 27° C.                                                                        Carboxyl content                                     ______________________________________                                        A          24,000        1.71                                                 B          20,000        2.47                                                 C          141,000       3.11                                                 ______________________________________                                    

Polymers A and B are poly(n-butyl acrylate) polymers, and polymer C is apoly(98% n-butyl acrylate-2% acrylic acid) polymer.

The polymers were used to prepare liquid vinylidene-terminatedpolyacrylate polymers. The procedure used follows that given in ExampleI. The recipes used and the data obtained are as follows:

    ______________________________________                                                         1      2       3                                             ______________________________________                                        Polymer A          100      --      --                                        Polymer B          --       100     --                                        Polymer C          --       --      40                                        Acetone            64       --      25.6                                      Glycidyl acrylate  7.8      8.8     5.0                                       Trimethyl amine, milliliters                                                                     0.8      --      0.35                                      DMP-30, milliliters                                                                              --       1.0     --                                        Temperature, ° C.                                                                         95       105     95                                        Time, hours        12       16      12                                        Vinylidene polymer, bulk                                                      viscosity, cps @ 27° C.                                                                   63,000   --      279,200                                   Residual carboxyl content                                                     weight percent     0.14     --      0.63                                      Percent carboxyl conversion                                                                      92       --      80                                        ______________________________________                                    

The polymers were cured using the following recipes:

    ______________________________________                                        Sample 2          100      --       --                                        Sample 3          --       100      --                                        Control.sup.1     --       --       100                                       Ethylenediamine   --       2.4      --                                        Triethylene tetraamine                                                                          --       --       0.6                                       Room temperature cure                                                         days               1       10        10                                       Hardness, Duro A  --       17       no                                        Elongation, percent                                                                             200      75       cure                                      ______________________________________                                         .sup.1 carboxylterminated poly(nbutyl acrylateethyl acrylateacrylic acid)

EXAMPLE VI

A liquid vinylidene-terminated polyether polymer was prepared from aliquid amine-terminated polyether. The amine-terminated polyether hasthe formula ##STR15## wherein x is from about 5 to 40. The polymer had avalue of x of about 30, a bulk viscosity at 27° C. of 236 cps., and aweight percent nitrogen content of 1.4 percent. The polymer was reactedat 100 parts by weight with 51.8 parts by weight of glycidyl acrylate in100 parts by weight of acetone, following the procedure given in ExampleI. The liquid vinylidene-terminated polyether polymer had a bulkviscosity at 27° C. of 500 cps. The vinylidene polymer was mixed at 100parts by weight with 3.5 parts by weight of ethylenediamine. After 10days at room temperature, the mix was a solid elastomer having a Duro Ahardness of 5 and a 30 percent elongation.

The liquid vinylidene polymers prepared from the amine-terminatedpolymers have the formula ##STR16## wherein R is defined as above and xis from 5 to about 40. The polymer prepared in the example has A equalto ##STR17## and x equal to 30.

I claim:
 1. A liquid vinylidene-terminated polymer having a molecularweight of from about 1000 to about 20,000 of the structure ##STR18##wherein B is a polymeric backbone of carbon-carbon, polyether, orpolysulfide linkages; Z is selected from the group consisting of --O--,--S--, --NH--, ##STR19## and --O--CH₂ --CH₂ --; A is a bivalent radicalselected from the group consisting of ##STR20## CH₂ --O--CH₂, and --CH₂--O--; and R is hyrogen or an alkyl radical containing 1 to 4 carbonatoms, said polymer having been vulcanized using a curative selectedfrom the group consisting of dithiols, polythiols, primary and secondaryamines, and primary and secondary polyamines.
 2. A vulcanized polymer ofclaim 1 wherein B consists of carbon-carbon linkages derived frompolymerized units of vinylidene monomer selected from the groupconsisting of (a) monoolefins containing 2 to about 8 carbon atoms, (b)dienes containing 4 to about 10 carbon atoms, (c) vinyl aromatics, (d)vinyl nitriles, (e) vinyl and allyl esters, (f) vinyl and allyl ethers,(g) divinyls and diacrylates, and (h) acrylates of the formula ##STR21##wherein R' is --H, --CH₃, or --C₂ H₅ and R" is selected from the groupconsisting of an alkyl radical containing 1 to 18 carbon atoms, analkoxyalkyl radical, an alkylthioalkyl radical, and a cyanoalkyl radicaleach containing 2 to about 12 carbon atoms.
 3. A vulcanized polymer ofclaim 2 wherein B consists of polymerized units of diene monomers, and Zis ##STR22##
 4. A vulcanized polymer of claim 3 wherein the dienemonomer is 1,3-butadiene and A is ##STR23##
 5. A vulcanized polymer toclaim 2 wherein B consists of polymerized units of butadiene andacrylonitrile monomers and Z is ##STR24##
 6. A vulcanized polymer ofclaim 2 wherein B consists of polymerized units of acrylate monomers andZ is ##STR25##
 7. A polymer of claim 6 wherein the acrylate monomer isn-butyl acrylate and A is ##STR26##
 8. A polymer of claim 1 of theformula ##STR27## wherein R is defined as above and x is from 5 to about40.
 9. A polymer of claim 8 wherein A is ##STR28## and x is
 30. 10. Avulcanized polymer of claim 1 wherein the curative is used incombination with 0.01 to about 3 parts by weight per 100 parts of saidliquid polymer of a tertiary amine cure catalyst.
 11. A vulcanizedpolymer of claim 8 wherein the curative employed is a thiol.